KR100776211B1 - Flame-retardant styrenic resin composition - Google Patents

Abstract

A flame retardant styrene-based resin composition is provided to reduce the content of a flame retardant and to improve flame retardancy, thermal stability and impact resistance. A styrene-based resin composition comprises 100 parts by weight of a styrene-based resin; 0.005-5 parts by weight of a radical generator selected from the group consisting of an oligomer type radical generator represented by the formula 1, a monomer type radical generator represented by the formula 2 and their mixture; and 0.1-30 parts by weight of a halogen compound, wherein R1 to R4 are identical or different one another and are a C1-C10 hydrocarbon group; and n is 2-7. Optionally the composition comprises further 0.1-10 parts by weight of antimony trioxide.

Description

Flame-retardant styrene resin composition {Flame-Retardant Styrenic Resin Composition}

Field of invention

The present invention relates to a flame retardant styrene resin composition. More specifically, the present invention relates to a flame-retardant styrene resin composition by introducing a radical generator into the styrene resin to significantly reduce the amount of flame retardant used compared to the prior art, excellent flame retardancy and impact resistance, and excellent thermal stability.

Background of the Invention

In general, styrene-based resins have good processability and mechanical strength, and are mainly used as exterior materials for electrical and electronic products. However, styrene-based resins are not resistant to sparks by themselves, and when sparks are ignited by external ignition factors, the resin itself is decomposed and provided as a raw material for fire, which may serve to further expand combustion. Therefore, in order to ensure the safety of fire, the necessity of the exterior materials of electrical and electronic products that satisfy the flame retardant standard is increasing.

Generally, as a method of imparting flame retardancy to a resin, there is an added flame retardant method in which a flame retardant and a flame retardant aid are added. Compounds containing halogen or phosphorus, which are mainly inert elements, are used as flame retardants, and antimony-containing inorganic compounds are used as flame retardants. In the case of styrene resins, halogen-containing organic compounds and antimony-containing inorganic compounds are mainly used to provide flame retardancy.

Flame retardant grades of resins include UL94 flame retardant grades and glow wire test (GWT) flame retardant grades, depending on the application. In Europe, GWT flame retardant grades are used rather than UL 94 flame retardant grades, such as wire / bulb sockets.

This GWT flame retardant rating specifies that the heated hot wire contacts the resin to extinguish the flames on the resin within a certain time. In the existing flame retardant technology, much research has been conducted in the technical direction to achieve the UL94 V-2 flame retardant grade, and a combination of a halogen flame retardant as a main flame retardant and antimony trioxide as a secondary flame retardant has been utilized.

The combination of the halogen-based flame retardant and antimony trioxide has an excellent flame retardant effect. However, a large amount of flame retardant must be used, and in particular, when using a halogen-based flame retardant having poor thermal stability, a situation in which thermal stability worsens when combined with antimony trioxide.

Therefore, the present inventors continued to overcome the problems of the prior art, as a result of using a halogen-based flame retardant to achieve GWT 960 ℃ with or without antimony trioxide and at the same time excellent flame resistance and thermal stability flame retardant styrene system It is early to develop a resin composition.

An object of the present invention is to provide a flame retardant styrene resin composition to which a radical generator is added.

Another object of the present invention is to provide a flame retardant resin composition excellent in impact resistance by reducing the flame retardant content.

Still another object of the present invention is to provide a flame retardant resin composition having excellent thermal stability.

The above and other objects of the present invention can be achieved by the present invention described below.

Summary of the Invention

Flame retardant styrene resin composition of the present invention (A) 100 parts by weight of styrene resin; (B) 0.005 to 5 parts by weight of a radical generator; (C) It consists of 0.1-30 weight part of halogen compounds.

The resin composition may further comprise 0.1 to 10 parts by weight of antimony trioxide (D).

Hereinafter, the content of the present invention will be described in detail below.

Detailed Description of the Invention

(A) styrene resin

The styrene resin according to the present invention is prepared by mixing a rubber and an aromatic monoalkenyl monomer and polymerizing it using a polymerization initiator.

The rubber is preferably 5 to 15% by weight of a rubber selected from the group consisting of butadiene rubbers, isoprene rubbers, copolymers of butadiene and styrene, alkyl acrylate rubbers and the like.

The aromatic monoalkenyl monomers include styrene, α-methyl styrene, vinyl toluene and the like.

In the present invention, one or more monomers selected from the group consisting of an alkyl ester monomer of acrylic acid or methacrylic acid and a vinyl cyanide compound may be further used together with the aromatic monoalkenyl monomer.

When using the aromatic monoalkenyl monomer alone or in addition to the aromatic monoalkenyl monomer, one or two or more monomers selected from the group consisting of alkyl ester monomers of acrylic acid or methacrylic acid and vinyl cyanide compounds, The total can be used in 85 to 95% by weight of the styrene resin (A).

As the polymerization initiator, one or two or more polymerization initiators selected from the group consisting of benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, and cumene hydroperoxide may be used.

Styrene-based resin of the present invention can be prepared using a bulk polymerization, suspension polymerization, emulsion polymerization or a mixture thereof, but is not necessarily limited thereto.

(B) radical generator

Radical generator used in the present invention is added to the styrene resin to promote the decomposition of the flame retardant and styrene resin to ensure a high flame retardancy, it is possible to reduce the amount of halogen flame retardant and antimony compound of the existing flame retardant and to reduce the price competitiveness It can be secured. In addition, the halogen compound and the antimony compound have a white color, and thus the brightness increases as the amount of use increases, which makes it difficult to realize a deep color of the product. Strength and colorability are increased.

In general, the radical generator generates radicals by decomposition of O-O bonds or C-C bonds, but in the case of O-O bonds, the decomposition temperature is low, so that the radical generator is decomposed in the extrusion and injection processing temperature ranges of the styrene-based resins and thus does not help flame retardation.

On the other hand, the radical generating agent having a CC bond used in the present invention has a half-life temperature of 250 ° C. or more and does not decompose under the extrusion and injection temperature conditions of the styrene-based resin, but decomposes during the combustion process, thereby ensuring processability and flame retardancy. It has advantages.

Among the radical generators having the C-C bond, the oligomeric radical generator used in the present invention may be represented by the following Chemical Formula 1.

[Formula 1]

Wherein R ₁ to R ₄ are hydrocarbons having 1 to 10 carbon atoms and are the same or different, and n is an oligomer type having 2 to 7 carbon atoms.

Among the radical generators having the C-C bond, the monomeric radical generator used in the present invention may be represented by the following Chemical Formula 2.

[Formula 2]

In the formula, R ₁ to R ₄ are hydrocarbons having 1 to 10 carbon atoms, and the same or different.

The oligomer-type radical generator is excellent in thermal stability during injection and extrusion processing compared to the monomer, but is somewhat expensive. In the present invention, an oligomeric radical generator and a monomeric radical generator are used alone or in combination, respectively.

Specific examples of the radical generator used in the present invention include poly 1,4-diisopropylbenzene, 2,3-dimethyl-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 4,5- Dimethyl-4,5-diphenyloctane, 2,3-dimethyl-2,3-di-p-tolylbutane, 3,4-dimethyl-3,4-di-p-tolylhexane, 2,3-dimethyl- 2, 3- diphenyl butane (dicumen) etc. are mentioned. Of these, poly 1,4-diisopropylbenzene and 2,3-dimethyl-diphenylbutane are most preferred.

In the present invention, the radical generator is preferably used in an amount of 0.005 to 5 parts by weight, and most preferably 0.05 to 3 parts by weight based on 100 parts by weight of the styrene resin (A). When the radical generator is used in an amount less than 0.005 parts by weight, the effect of improving flame retardancy is not great. When the radical generator is used in an amount of more than 5 parts by weight, gas generation during injection and extrusion may occur, and dripping due to resin decomposition may occur. .

By the use of the radical generator, it is possible to induce the reduction of the flame retardant and to improve the impact strength, and also to improve the colorability according to the reduction of the antimony trioxide used as the auxiliary flame retardant.

(C) halogen-based compound

In the present invention, a halogen compound is used as the flame retardant. The halogen compound contains a halogen element, that is, bromine or chlorine, and its content is suitably 50% or more.

The halogen compounds usable in the present invention are decabrominated diphenyl ether, decabromodiphenyloxide, decabromodiphenylethane, decabromodiphenylether, tetrabromobisphenol A, tetrabromobisphenol A-epoxy oligomer, hexa Bromocyclododecane, brominated epoxy oligomers, octabromotrimethylphenylindan, ethylene bistetrabromophthalimide, 2,4,6-tris (2,4,6-tribromophenoxy) -1 , 3,5-triazine and 1,2,3,4,7,8,9,10,13,13,14,14-dodecachloro-1, 4, 4a, 5, 6, 6a, 7, 10, 10a, 11, 12, 12a-dodecahydro-1, 4, 7, 10- dimethanodibenzo (a, e) cyclooctene, etc. are mentioned.

In the present invention, the halogen compound is preferably used in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the styrene resin (A). If the halogen compound is used in less than 0.1 parts by weight, the flame retardant effect does not appear well, and when it is used in excess of 30 parts by weight, physical properties such as workability and mechanical strength are deteriorated.

(D) antimony trioxide

Antimony trioxide in the present invention is optionally used as a flame retardant adjuvant for improving the flame retardancy of the halogen compound. As for the said antimony trioxide, it is preferable to use 0.1-10 weight part with respect to 100 weight part of (A) styrene resins. If the antimony trioxide is used in an amount less than 0.1 parts by weight, it is difficult to expect a flame retardant synergistic effect.

In the flame retardant styrene resin composition of the present invention, antioxidants, impact modifiers, heat stabilizers, lubricants, fillers, coupling agents, antistatic agents, dispersants, plasticizers, pigments, dyes and mixtures thereof, etc., in addition to the additives according to the purpose of use of the produced product. This amount can be added.

The invention can be better understood through the following examples, which are intended for purposes of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Examples and Comparative Examples

The specification of the material used in the Example and comparative example of this invention is as follows.

(A) styrene resin

Cheil Industries' impact polystyrene, HG-1760HA (HIPS-1) and HI-1190 (HIPS-2), were used in combination.

(B) radical generator

Poly diisopropyl benzene (RG-1) and 2,3-dimethyl-2,3-diphenyl butane (RG-2) were used.

(C) halogen compounds

Brominated epoxy oligomer (HR-1), 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine (HR-2), 1,2 , 3,4,7,8,9,10,13,13,14,14-dodecachloro-1, 4, 4a, 5, 6, 6a, 7, 10, 10a, 11, 12, 12a -dode Carhydro-1, 4, 7, 10-dimethanodibenzo (a, e) cyclooctene (HR-3) and hexabromocyclododecane (HR-4) were used.

(D) antimony trioxide

Ilsung antimony ANTIS N, antimony trioxide was used.

Example  1-11 and Comparative Example  1-11

The above-mentioned (A) styrene resin, (B) radical generator, (C) halogen compound, and (D) antimony trioxide are mixed according to the composition of each component shown in Tables 1 and 2, followed by a conventional biaxial Extruder was extruded at a temperature range of 190 to 220 ℃ to prepare a pellet. The prepared pellets were dried at 70 ° C. for 3 hours and then injected into a 6 Oz injection machine under conditions of a molding temperature of 180 to 220 ° C. and a mold temperature of 30 to 50 ° C. to prepare a physical specimen.

The flame retardancy of the prepared specimens was UL94 746A and GWT (960 ℃), and thermal stability was measured by the TGA (Thermal gravity analyzer) at a temperature increase rate of 20 ℃ / min at an initial temperature loss of 3% decomposition temperature, The results are shown in Tables 1 and 2 below.

TABLE 1

TABLE 2

Through Examples and Comparative Examples of Tables 1 and 2, it is possible to prepare a resin having excellent flame retardancy and thermal stability even when using a radical generator and selectively using antimony trioxide while reducing the content of halogen-based flame retardant. Able to know.

The present invention has the effect of providing a flame retardant styrene resin composition excellent in flame retardancy and heat stability by reducing the content of the flame retardant by using a radical generator.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (6)

(A) 100 parts by weight of styrene resin; (B) 0.005 to 5 parts by weight of a radical generator; And (C) 0.1 to 30 parts by weight of a halogen compound; (B) the radical generator is flame-retardant, characterized in that selected from the group consisting of oligomer-type radical generator represented by the following formula (1), monomeric radical generator represented by the following formula (2) and mixtures thereof Styrene-based resin composition: [Formula 1]

Wherein R ₁ to R ₄ are hydrocarbons having 1 to 10 carbon atoms and are the same or different, and n is 2 to 7; [Formula 2]

In the formula, R ₁ to R ₄ are hydrocarbons having 1 to 10 carbon atoms, and the same or different. The flame retardant styrene resin composition according to claim 1, further comprising 0.1 to 10 parts by weight of antimony trioxide (D). delete The method of claim 1, wherein the (B) radical generator is poly 1,4-diisopropylbenzene, 2,3-dimethyl-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 4, 5-dimethyl-4,5-diphenyloctane, 2,3-dimethyl-2,3-di-p-tolylbutane, 3,4-dimethyl-3,4-di-p-tolylhexane and 2,3- Flame-retardant styrene resin composition is selected from the group consisting of dimethyl-2,3-diphenylbutane (dicumene). The said (C) halogen compound is a decabrominated diphenyl ether, decabromodiphenyl oxide, decabromo diphenyl ethane, decabromo diphenyl ether, tetrabromobisphenol A, tetrabromobisphenol A -Epoxy oligomers, hexabromosa cyclododecane, brominated epoxy oligomers, octabromotrimethylphenylindan, ethylene bistetrabromophthalimide, 2,4,6-tris (2,4,6-tribromophenoxy C) -1,3,5-triazine and 1,2,3,4,7,8,9,10,13,13,14,14-dodecachloro-1, 4, 4a, 5, 6, 6a, 7, 10, 10a, 11, 12, 12a-dodecahydro-1, 4, 7, 10-dimethanodibenzo (a, e) cyclooctene and mixtures thereof Flame retardant styrene-based thermoplastic resin composition. The method of claim 1, wherein the resin composition further comprises an additive selected from the group consisting of antioxidants, impact modifiers, heat stabilizers, lubricants, fillers, coupling agents, antistatic agents, dispersants, plasticizers, pigments, dyes and mixtures thereof. Flame retardant styrene-based thermoplastic resin composition, characterized in that.